Hexanitrate

Pentaerythritol may be nitrated by a batch process at 15.25°C using concentrated nitric acid in a stainless steel vessel equipped with an agitator and cooling coils to keep the reaction temperature at 15—25°C. The PETN is precipitated in a jacketed diluter by adding sufficient water to the solution to reduce the acid concentration to about 30%. The crystals are vacuum filtered and washed with water followed by washes with water containing a small amount of sodium carbonate and then cold water. The water-wet PETN is dissolved in acetone containing a small amount of sodium carbonate at 50°C and reprecipitated with water the yield is about 95%. Impurities include pentaerythritol trinitrate, dipentaerythritol hexanitrate, and tripentaerythritol acetonitrate. Pentaerythritol tetranitrate is shipped wet in water—alcohol in packing similar to that used for primary explosives. 

Manufacture of vitamin C starts with the conversion of sorbitol to L-sorbose. Sorbitol and xyHtol have been used for parenteral nutrition following severe injury, bums, or surgery (246). An iron—sorbitol—citric acid complex is an intramuscular bematinic (247). Mannitol administered intravenously (248) and isosorbide administered orally (249) are osmotic diuretics. Mannitol hexanitrate and isosorbide dinitrate are antianginal dmgs (see Cardiovascular agents). 

Mannitol hexanitrate [15825-70-4] M 452.2, m 112-113". Crystd from EtOH. EXPLOSIVE (on detonation). 

Ignition element for lighter, containing pyrophoric liquid Inositol hexanitrate (dry)... 

Historical. The action of nitric acid on mannitol was first examined by A. Sobrero who isolated the hexanitrate in 1847 (Ref 3). The prepn on a lab scale was repeated by other workers in the mid-19th century (Refs 2, 4,10 12). It was mfd on a small scale in the Royal Arsenal at Turin, Italy until 1853, when 400g expld with great damage (Ref 33, p 198) later work has been described in Refs 13 15... 

Chemical Reactions. Mannitol is regenerated by treatment of the hexanitrate with Amm sulfide (Ref 6), iron in acet ac (Ref 7), ferric chloride (Ref 14), or with hydrogen iodide... 

Analytical. Mannitol Hexanitrate can be hydrolyzed in basic soln and the soln acidified in the presence of NITRON to quanty ppt NITRON nitrate (Ref 16). A procedure is described for. the quant detn of nitrate esters, including Mannitol Hexanitrate, in the presence of aromatic nitro compds in Ref 17. It gives a yellow color when treated in et ale or acet with 5% aq K hydroxide, then 5% aq ammonia (Ref 24), It can be quanty detd by reduction with Devarda s alloy (Encycl 5, D-l 110) or A1 wire in aq et ale and titration of the evolved... 

Specific Volume of Gases Formed on Explosion. 723ml/g (NG 712ml) (Ref 46) Stabilization. Chromatographically pure Mannitol Hexanitrate was mixed with varying percentages of 22 stabilizers and the mixts tested for stability in the 100° heat test best results were obtained with a mixt of 96% MHN, 2% Amm oxalate, and 2% dicyandiamide (4.07% wt loss after 48 hours, 5.74% after 96 hours) (Ref 56). The use of ethylene oxide as a stabilizer is reported in Ref 27 Thermal Decomposition. Slow heating causes decompn at 150° with evolution of red fumes (Ref 20, p 249)... 

On nitration, oxanilide yields expl tetra- and hexanitrates (see below)... 

With a TEA detector, SFC can detect a number of explosives including nitroglycerine, EGDN, PETN, mannitol hexanitrate, RDX, HMX, TNT, tetryl,... 

The above mechanism of intramolecularly catalyzed cleavage is possible only for compounds with a N02 group close to the departing NO group. In other words, it can be postulated to follow nitro reduction in erythritol tetra-nitrate (9.8), mannitol hexanitrate (9.9), pentaerythritol tetranitrate (9.10), and perhaps trolnitrate (9.14), but not in isosorbide dinitrate (9.11). 

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